Complex metal azo compounds



Patented Oct. 5, 1937 COMPLEX METAL AZO COMPOUNDS Hermann Winkeler, Ludwigshafen-on-the-Rhine,

and Erich Fischer, Bad Soden in Taunus, Germany, assignors to General Aniline Works,

Inc., New York, N. Y., a

ware

corporation of Dela- No Drawing. Original application January 21,

1935, Serial No. 2,796.

Divided and this application November 23, 1935, Serial No. 51,274. In Germany January 31, 1934 8 Claims.

This invention relates to the production of complex metal compounds of new azo dyestufis and a process of producing the same. The present application has been divided out from our copending application Ser. No. 2,796, filed January 21, 1935.

We have found that valuable azo dyestufis capable of being converted in substance or on the fibers into complex compounds are obtained by coupling with coupling components diazo compounds of amines of the general formula:

H2NA-so2-NH-B in which A stands for the radicle'of an aromatic hydrocarbon which may also contain substituents selected from the group consisting of a halogen atom, the N02- and an -Oalkyl group, B stands for a hydrocarbon radicle of the benzene series containing the hydroxy group in 2-position with reference to the carboxylic group as in l-position and which in the 5-position may contain a. methyl group or a substituent selected from the group consisting of the halogen, -NO2 and -HSO3 group, the said hydrocarbon radicle of the benzene series being attached to the sulfonyl amide-grouping in the 3-position to the carboxylic group.

Suitable amines of the said kind are for example N- (3'-aminobenzene-sulfonyl) -3-amino- 2 hydroxybenzene 1 carboxylic acid, N- (3'- aminobenzene-sulfonyl) 3 amino-Z-hydroxy-S- sulfobenzene l-carboxylic acid, N-(3-amino-6'- methylbenzene sulfonyl) -3-amino-2-hydroxy-5- sulfobenZene-l-carboxylic acid, N-(4-amino-3'- 'chlorobenzene-sulfonyl) 3 amino-2-hydroxy-5- sulfobenzene-l-carbo-xylic acid, N- (3 -amino-4'- methoxybenzene-sulfonyl) -3-amino -2- hydroxy- 5-sulfobenzene-l-carboXylic acid, N-(3-aminobenzene-sulionyl) 3 amino 2-hydroxy-5-nitrobenzene 1 carboxylic acid, N-(3'-amino-6- methylbenzene sulfonyl) -3amino-2-hydroxy5- methylbenzenel-carbo-xylic acid.

The dyestufis obtainable according to the invention from aminosulfonyl compounds of orthoaminosalicylic acids yield complex chromium compounds which have good properties as re ards fastness to light, washing, fulling, rubbing and alkali. The y s uf s. themselves as well as their complex chromium compounds have a very good levelling power.

The following examples will further illustrate the nature of this invention but the invention is not restricted to these examples. The parts are by weight.

' Example 1 388 parts of. N-(3-amino-benzene-sulfonyl) 3-amino-2- hydroxy-5-sulfo benzenel-carboxylic acid' are dissolved in 2000 parts of water with an addition of sodium carbonate and mixed with 69 parts'of sodium nitrite. The whole is allowed to flow into diluted hydrochloric acid at room temperature. The separated white-gray diazo compound is then carried into an ice-cooled solution of 103 parts of 3-methyl-5-pyrazolone rendered alkaline with sodium bicarbonate. At the end of the coupling the dyestuff being already partly separated is totally salted out and filtered by suction. The dy estufi dyes Wool very uniformly yellow shades with a tint of green whichyields dyeings very fast to light, washing and fulling by aftertreatment with chromium salts. The complex chromium compound of the dyestuff obtained by treating the dyestuff in substance with agents supplying chromium has quite an excellent levelling, power and yields on animal fibres dyeing of good fastness to light washing and fulling.

Using the diazo compound of N-(3'-amino-6- methylbenzene-sulfonyl) -3-amin.o-21-hydroxy-'5- sulfoloenzene-l-carboxylic acid or N-(P-amino- 3- chlorobenzene-sulfonyl) -3-amino-2-hydroxy- 5-sulfobenzene-l-carboxylic acid instead of the above mentioned diazo compound, dyestuffs of similar properties are obtained. These dia zo compounds when coupled with other pyrazolones than 3-methyl-5-pyrazolone, for example 1- phenyl-3emethyl-5-pyrazolone or 1(2-chlorophenyl)-3-methyl-5-1oyrazolone, yield dyestuffs which dye more reddish shades of better'fastness to washing and fulling than those obtained by coupling the said diazotized amines with 3- methyI-E-pyrazolone.

Example 2 322 parts of N-(3'-amino.benzene-sulfonyl) -3- amino-2rhydroxy fa-methylbenzene 1- carboxylic acidare diazotized as described inExamplel and the diazo compound is coupled with 1-(2'-ch1oro..

shades of very good fastness to light and good fastness to washing and fulling. a 7

Using N (3' amino 6 methylbenzene-sulfonyl) 3 amino-2-hydroXy-5- methylbenzene 1- carboxylic acid for the diazo compound dyestufis of similar properties'are obtained; By coupling amino-2-hydroxy .benzene-I-carboxylic,acid iare the said diazo compounds with sulfonated pyrazolones free from halogen the azo'dye'stufis obtained dye somewhat more reddish shades. H

Examples". 7 .i

388 parts of N (3-aminobenzene-sulfonyl)-3 amino-2-hydroxy-5-sulfobenzene 1 carboxylic acid are diazotized as described in Example 1 and coupled with 2.4;dihydroxy -quinoline in a solution rendered alkaline with sodium carbonate. The dye stuff; obtained yields on wool and silk, either by after-treatment the dyeing onethe fibre with agents supplying chromium or by dyeing With'the complex chromium' compound of the dyestuff, yellow shades of good fastness. pling the said diazo compound with beta-naphtholor beta-naphthol-sulfonic acids dyestuifs are obtained-Whichdye orange to red shades. When using resorcinol as coupling compound, a dyestuif' is obtained which dyes 7 leather yellow-brown shades having a very good fastness to light.

' I) ,7. j sam e? r 308 .parts of N-(Bamino-be nzenesulfonyl1+3- idiazo'tize'd as described in Example land mixed withasolution of 310 parts of, l-,( 2'-chlor-5'- sulpho-phenyl) -3.-methyl-.5-pyra zolone g rendered alkaline with sodium bicarbonate. 'I he dyestufi is isolated by salting' outand dyes wool'yellow shades. .By. after-treatment with, chromium salts yellow dyeings of good, fastness to washing and fulling, are obtained. The chromium com pound obtained'by chroming the dyestuff itself dyes wool and silk very uniformly yellow shades .of good f astness to washing and fulling.

What we claim is: v

1. Complex metal compounds of azo dyestufis corresponding to the general'formula ,o s

7 /H Xr-N=N? 2 W "Q 0 P in which A stands for a radicle selected from the group consisting of aromatic hydrocarbons, halogenated aromatic hydrocarbons, nitrated 'aro matic hydrocarbons and alkoxy. substituted are matic hydrocarbons, B stands for a hydrocarbon radicle of the benzene series containing the hydroxy group in the 2-position with reference to the carboxylic group in the 1-position and which contains in the -position a member of the group consisting of hydrogen, methyl, halogen, the N02 and-SOaI-I group, the said-hydrocarbon radicle of the benzene series being attached to the'sulfonyl- V amide grouping. in the 3 -position with'reference to thecarboxylic acid group, and'whereinXrepresents a coupling component selected fromthe By cou- 'SOaH group consisting of pyrazolones, hydroxy-quinolines and phenols.

2. Complex chromium compounds of azo dye- 1 stuffs corresponding to the general formula OH XN=N--ASOzNH-B COOH in which A standsffor a radicle'selected from the group consisting of aromatic hydrocarbons, halogenated aromatic hydrocarbons, nitrated arol matic hydrocarbons and alkoxy substituted aromatic hydrocarbons, B stands for a hydrocarbon V radicle of the benzene series containing the hydroxy group, in the 2-p'osition with reference to the carboxylic' group in the 1-position and which contains in the 5-position a member of the group 7 consisting of hydrogemmethyl, halogen, the N02- and-SO3H group, the said hydrocarbon radicle of the benzene series being attached to the sulfonyl- I amide grouping in the 3-position with reference to the carboxylic acid group, and wherein X represents a coupling component selected from the group consisting of pyrazolones, hydroxy-quinolines and phenols. v

' 3. Complex metal compounds of an azo dyestuff corresponding to the formula: V

Complex chromium compound of an azo dyestuff corresponding to'the formula:

' 5 Complex metal I compounds of ;an

stuff corresponding to the formula:

6. Complex chromium compound of 7 an azo dyestuff corresponding to theformula: 7

'7. Complex metal compounds of an azo dyestuif corresponding to the formula:

V 7 $0.11 8. Complex chromium compound of an azo dyestuff corresponding to the formula:

I 7 :HEBQMANN IN ELER,

' ERICH FISCHER? azodye- 

